85390-90-5

Upstream product

• 2043-61-0 cyclohexanecarbaldehyde 

Downstream Products

• 65826-85-9 (Diiodomethyl)cyclohexane 
• 23904-33-8 (iodomethylene)cyclohexane 
• 65826-86-0 (Bromoiodomethyl)cyclohexane 
• 86328-83-8 cyclohexyldiazomethane 
• 1618681-23-4 (5-cyclohexylpent-1-yn-1-yl)benzene 
• 4569-36-2 4-cyclohexyl-1-butene 

Relevant academic research and scientific papers

Ruthenium catalyzed β-selective alkylation of vinylpyridines with aldehydes/ketonesviaN2H4mediated deoxygenative couplings

Umpolung (polarity reversal) tactics of aldehydes/ketones have greatly broadened carbonyl chemistry by enabling transformations with electrophilic reagents and deoxygenative functionalizations. Herein, we report the first ruthenium-catalyzed β-selective alkylation of vinylpyridines with both naturally abundant aromatic and aliphatic aldehyde/ketonesviaN2H4mediated deoxygenative couplings. Compared with one-electron umpolung of carbonyls to alcohols, this two-electron umpolung strategy realized reductive deoxygenation targets, which were not only applicable to the regioselective alkylation of a broad range of 2/4-alkene substituted pyridines, but also amenable to challenging 3-vinyl and steric-embedded internal pyridines as well as their analogous heterocyclic structures.

Palladium-Catalyzed Defluorinative Alkylation of gem-Difluorocyclopropanes: Switching Regioselectivity via Simple Hydrazones

Conventional approaches for Pd-catalyzed ring-opening cross-couplings of gem-difluorocyclopropanes with nucleophiles predominantly deliver the β-fluoroalkene scaffolds (linear selectivity). Herein, we report a cooperative strategy that can completely switch the reaction selectivity to give the alkylated α-fluoroalkene skeletons (branched selectivity). The unique reactivity of hydrazones that enables analogous inner-sphere 3,3′-reductive elimination driven by denitrogenation, as well as the assistance of steric-embedded N-heterocyclic carbene ligand, are the key to switch the regioselectivity. A wide range of hydrazones derived from naturally abundant aryl and alkyl aldehydes are well applicable, and various gem-difluorocyclopropanes, including modified pharmaceutical and biological molecules, can be efficiently functionalized with high value alkylated α-fluorinated alkene motifs under mild conditions.

Submonomer synthesis of peptoids containingtrans-inducingN-imino- andN-alkylamino-glycines

The use of hydrazones as a new type of submonomer in peptoid synthesis is described, giving access to peptoid monomers that are structure-inducing. A wide range of hydrazones were found to readily react with α-bromoamides in routine solid phase peptoid submonomer synthesis. Conditions to promote a one-pot cleavage of the peptoid from the resin and reduction to the correspondingN-alkylamino side chains were also identified, and both theN-imino- andN-alkylamino glycine residues were found to favor thetrans-amide bond geometry by NMR, X-ray crystallography, and computational analyses.

Switch in Selectivity for Formal Hydroalkylation of 1,3-Dienes and Enynes with Simple Hydrazones

Controlling reaction selectivity is a permanent pursuit for chemists. Regioselective catalysis, which exploits and/or overcomes innate steric and electronic bias to deliver diverse regio-enriched products from the same starting materials, represents a powerful tool for divergent synthesis. Recently, the 1,2-Markovnikov hydroalkylation of 1,3-dienes with simple hydrazones was reported to generate branched allylic compounds when a nickel catalyst was used. As part of the effort, shown here is that a complete switch of Markovnikov to anti-Markovnikov addition is obtained by changing to a ruthenium catalyst, thus providing direct and efficient access to homoallylic products exclusively. Isotopic substitution experiments indicate that no reversible hydro-metallation across the metal-π-allyl system occurred under ruthenium catalysis. Moreover, this protocol is applicable to the regiospecific hydroalkylation of the distal C=C bond of 1,3-enynes.

Safe and Facile Access to Nonstabilized Diazoalkanes Using Continuous Flow Technology

Despite the high synthetic potential of nonstabilized diazo compounds, their utilization has always been hampered by stability, toxicity, and safety issues. The present method opens up access to the most reactive nonstabilized diazoalkanes. Among diazo compounds, nonstabilized alkyl diazo compounds are the least represented because of their propensity to degrade during preparation. The continuous flow oxidation process of hydrazones on a silver oxide column afforded an output stream of base- and metal-free pure diazo solution in dichloromethane. Starting from innocuous ketones and aldehydes, this methodology allows the production of a broad range of unprecedented diazoalkanes compounds in excellent yields, while highlighting their synthetic potential and the possibility of safe large-scale diazo production.

Umpolung of Carbonyl Groups as Alkyl Organometallic Reagent Surrogates for Palladium-Catalyzed Allylic Alkylation

Palladium-catalyzed allylic alkylation of nonstabilized carbon nucleophiles is difficult and remains a major challenge. Reported here is a highly chemo- and regioselective direct palladium-catalyzed C-allylation of hydrazones, generated from carbonyls, as a source of umpolung unstabilized alkyl carbanions and surrogates of alkyl organometallic reagents. Contrary to classical allylation techniques, this umpolung reaction utilizes hydrazones prepared not only from aryl aldehydes but also from alkyl aldehydes and ketones as renewable feedstocks. This strategy complements the palladium-catalyzed coupling of unstabilized nucleophiles with allylic electrophiles by providing an efficient and selective catalytic alternative to the traditional use of highly reactive alkyl organometallic reagents.

Photochemistry of Alkyl Halides. 9. Geminal Dihalides

The photobehavior of the geminal dihalides (diiodomethyl)cyclohexane (7), (bromoiodomethyl)cyclohexane (11), (dibromomethyl)cyclohexane (17), (diiodomethyl)cyclopentane (22), 3,3-dimethyl(diiodomethyl)cyclobutane (27), and 8,8-diiodo-2,6-dimethyl-2-octene (31) has been studied and compared with that previously observed for diiodomethane.In all solvents the corresponding vinyl halides (iodomethylene)cyclohexane (13), (bromomethylene)cyclohexane (21), (iodomethylene)cyclopentane (23), 3,3-dimethyl(iodomethylene)cyclobutane (28), or cis- and trans-3,7-dimethyl-1-iodo-1,6-octadiene (33) were obtained, which are thought to arise from α-halo cationic intermediate formed via initial light-induced homolytic cleavage of the carbon-iodine bond followed by electron transfer within the resulting caged radical pair, as shown in Schemes II and III.In the case of diiodide 31 competing intramolecular trapping of the α-iodo cation afforded in addition the cyclized isopulegyl iodide (34).In polar solvents the vinyl iodides were accompanied by the nonhalogenated products methylenecyclohexane (15), 1-methylcyclopentene (25), cyclohexene (26), 4,4-dimethylcyclopentene (29), and cis- and trans-carane (35), which are thought also to arise from the α-halo cationic intermediate. 1.1-Diiodo-2,2-dimethylpropane (1b) afforded 2-methyl-2-butene (6b).Except for carane (35) from diiodide 31 there was no detectable formation of cyclopropanes.In methanol the nucleophilic substitution products (dimethoxymethyl)cyclohexane (14), (dimethoxymethyl)cyclopentane (24), and 1,1-dimethoxy-2,2-dimethylpropane (30) were obtained.It is concluded that geminal dihalides undergo predominant, if not exclusive, photoreaction via initial clea vage of a single carbon-halogen bond in analogy with monohalides and that carbene intermediates are not formed.A similiar conclusion has been reached previously for diiodomethane in the photocyclopropanation of alkenes.